Mechanical activation of olivine

This paper investigates how mechanical activation of olivine can increase the mineral’s surface reactivity, and illustrates how such technology can give rise to new or improved olivine products. The olivine material used in this study consisted of pure olivine crystals (Mg_1.860Fe_0.134Ni_0.006SiO₄) originating from North Cape Minerals dunite deposit at Åheim in Western Norway. Following activation in a planetary mono mill, the activated olivine products were visually inspected using scanning electron microscopy (SEM) and characterised with respect to particle size, specific surface area (BET) and X-ray diffraction (XRD) signature. The surface reactivity of the activated olivine products was determined through simple acid leaching experiments in which the initial acid consumption rates were determined. The initial phase of olivine dissolution could be modelled using first order kinetics. Prolonged dry milling of pure olivine crystals resulted in highly aggregated products that were more reactive with respect to dissolution in acid than their respective BET surface areas would suggest. Relative to olivine that had been milled for 1 min, 60 min of milling increased the initial reaction rate by a factor of 9.0, whereas the corresponding increase in specific surface area was 1.8. The results from both the leaching experiments and the XRD analysis suggest that the observed over-proportional increase in reactivity with respect to surface area is largely due to structural disordering (i.e. mechanical activation) of the olivine surfaces.     

A study of atmospheric acid leaching of a South African nickel laterite

Nickel and cobalt acid leaching from a low-grade South African saprolitic laterite using sulphuric acid was studied. Ore characterisation was performed by XRD and XRF. Batch agitation leaching tests were conducted at atmospheric pressure investigating main parameters: particle size and percent solids at 25 °C and 90 °C. Ore characterisation showed that the ore is a saprolitic laterite with nickel present in lizardite. Leaching tests showed that nickel and cobalt could be leached from the ore at atmospheric pressure. Nickel was found to be more leachable from the coarser −106 + 75 μm fraction, with 98% Ni being extracted at 90 °C after 480 min. Cobalt was not favoured by variation in particle size and increased percent solids. Increasing ore percent solids improved nickel extraction at 25 °C however at 90 °C extraction decreased due to a diffusion layer build-up as a result of amorphous colloidal silica. The co-dissolution of magnesium and iron was elucidated. Nickel leaching data at increased temperature and percent solids fit the shrinking core model equation, k_dt = 1−2/3x − (1 − x)^2/3 showing that nickel leaching reaction was diffusion controlled under the set conditions.     

Modification of ilmenite surface properties by superficial dissolution method

Acid surface dissolution as a pretreatment method converts Fe²⁺ ions on the ilmenite surface to Fe³⁺ ions. XPS analysis showed that the content of Fe³⁺ increases from 48.5% to 59.8% after surface dissolution for 15 min in a solution of sulfuric acid with a concentration of 10%. This conversion, without any phase transformation, decreases the zeta potential of ilmenite in a wide pH range, resulting in a shift in IEP (Iso-Electric Point) from a pH of 5.4 to 2.3. FTIR spectra and zeta potential measurements showed that the increase of oleate ions adsorption on the ilmenite surface, resulting from the surface dissolution process, is insignificant. After surface dissolution, the formation of more ferric iron oleate species (Ksp = 10^−29.7) being more stable than ferrous iron oleate (Ksp = 10^−15.5) compounds yields an increase of ilmenite hydrophobicity and floatability in a wide pH range. Using 3.65 × 10⁻⁴ M sodium oleate at a pH of 6.3, the maximum flotation recoveries are obtained as 73.5% and 92% for non-treated and acid pretreated ilmenite, respectively.     

Copper leaching from waste electric cables by biohydrometallurgy

This study examines the leaching of copper from waste electric cables by chemical leaching and leaching catalysed by Acidithiobacillus ferrooxidans in terms of leaching kinetics and reagents consumption. Operational parameters such as the nature of the oxidant (Fe³⁺, O₂), the initial ferric iron concentration (0–10 g/L) and the temperature (21–50 °C) were identified to have an important influence on the degree of copper solubilisation. At optimal process conditions, copper extraction above 90% was achieved in both leaching systems, with a leaching duration of 1 day. The bacterial leaching system slightly outperformed the chemical one but the positive effect of regeneration of Fe³⁺ was limited. It appears that the Fe²⁺ bio-oxidation is not sufficiently optimised. Best results in terms of copper solubilisation kinetics were obtained for the abiotic test at 50 °C and for the biotic test at 35 °C. Moreover, the study showed that in same operating conditions, a lower acid consumption was recorded for the biotic test than for the abiotic test.     

Review of rate constants for thiosulphate leaching of gold from ores,concentrates and flat surfaces: Effect of host minerals and pH

A review of literature data for different types of sulphide concentrates and gold ores has been carried out to examine the impact of host minerals and pH upon gold leaching. Analysis of initial rate data over the first 30–60 min of gold leaching from sulphide concentrates or silicate ores over a range of ammonia, thiosulphate, and copper(II) concentrations, pH (9–10.5) and temperatures up to 70 °C shows the applicability of a shrinking sphere kinetic model with an apparent rate constant of the order k_ss = 10⁻⁶–10⁻³ s⁻¹. The dependence of apparent rate constant on pH and initial concentrations of copper(II) and thiosulphate is used to determine a rate constant k_Au(ρr)⁻¹ of the order 1.0 × 10⁻⁴–7.4 × 10⁻⁴ s⁻¹ for the leaching of gold over the temperature range 25–50 °C (ρ = molar density of gold, r = particle radius). These values are in reasonable agreement with rate constants based on electrochemical and chemical dissolution of flat gold surfaces: k_Au = 1.7 × 10⁻⁴–4.2 × 10⁻⁴ mol m⁻² s⁻¹ over the temperature range 25–30 °C. The discrepancies reflect differences in surface roughness, particle size and the effect of host minerals.     

Kinetics of saprolitic laterite leaching by sulphuric acid at atmospheric pressure

Mineralogical analyses of the saprolitic laterite material have been characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermal analysis, scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDAX). Results showed that the saprolitic laterite material consists mainly of nickel-substituted lizardite showing the pebble-like morphology and traces of magnetite and phlogopite. Leaching results showed that as much as 84.8% nickel could be leached under the experimental conditions of 10% (v/v) H₂SO₄, 90 °C reaction temperature, leached within 5 min, particle size d₅₀ = 25 μm, stirring at 500 rpm and liquid to solid ratio 3:1. The kinetics of nickel and magnesium leaching from the saprolitic laterite material have been investigated in a mechanically stirred reactor and the activation energies were determined to be 53.9 kJ mol^?1 for nickel and 59.4 kJ mol^?1 for magnesium respectively, which are characteristic for a chemical reaction controlled process. The similarity of the activation energies of nickel and magnesium leaching from the saprolitic laterite material by sulphuric acid means that nickel in lizardite is loosely bound within the octahedral layer and almost all of the nickel could be leached simultaneously with magnesium but without complete decomposition of the silicate structure.     

Bioleaching of djurleite using Acidithiobacillus ferrooxidans

The bioleaching of djurleite using Acidithiobacillus ferrooxidans (LD-1) was investigated in this paper. Experiments were carried out in shake flasks at pH 2.0, 160 r/min and 30 °C. The leaching residues were analyzed using X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The total copper extraction of djurleite under optimal condition reached 95.12%. The XRD analysis indicated the residues mainly consisted of ammoniojarosites and S₈. It was observed by the SEM image that the djurleite was heavily etched. The XPS results confirmed the intermediate product formed during djurleite leaching was CuS. The result indicates the reaction pathway is: Cu₃₁S₁₆ → CuS → tCu²⁺ and S⁰.     

Effect of water quality on the leaching of a low-grade copper sulfide ore

Copper extractions from a low-grade, ground copper sulfide ore (0.7% Cu) leached in three media were freshwater < seawater > double-strength seawater and pH 1.5 ⩾ pH 2; 84% extraction was achieved in pH 1.5 seawater in 28 days at 23 °C. Cu-oxide and carbonate dissolved completely and chalcocite was altered to secondary covellite, some of which persisted in all media for the duration of the 28-day experiment. Chalcopyrite and bornite were both oxidised more readily in saline water. Iron, sodium, potassium and sulfur (sulphate) concentrations in leach solutions diminished and the amounts of insoluble iron(III) reaction products increased with increased salinity and increased solution pH. While, overall, silicate dissolution was small, the amounts of poorly crystalline phases (both iron(III) and silica-rich phases) increased with increased salinity and were greater in pH 1.5 media. In the context of heap leaching, the increased amounts of secondary precipitates formed if saline water was used could result in lower extraction efficiency and the increased total dissolved solids, density and viscosity could result in increased energy costs for solution management at operations.The software package Geochemist’s Workbench was evaluated by modelling the synthetic seawater – pH 2 test. It was possible to predict the evolution of the solution composition, the main species and phase boundaries at the start and end of leaching, and the formation of three reaction products in accord with experimental data by applying the React sliding function.The tests were conducted using a pulverised ore sample to increase dissolution reaction kinetics, particularly for chalcopyrite. Future tests should be conducted using ore particle sizes appropriate to heap leaching. The copper distribution within particles indicated that the test ore may not be suited to heap leaching because the surface exposure of copper sulfide grains is limited. Therefore reactor designs better suited to smaller sized particles with/without pre-treatment should be considered.     

Effect of mechano-chemical activation on bioleaching of Indian Ocean nodules by a fungus

The effect of mechano-chemical activation of Indian sea nodules, while recording the zeta potential, particle size distribution and surface area, on the bio-dissolution of metals by Aspergillus niger has been investigated. Activation is a term used to indicate what takes place when increasing grinding time does not result in significant change in particle size but rather results in the accumulation of energy that may lead to the development of lattice defects within the particles that can aid biological attack. It was observed that the mechano-chemical activation improved the bio-dissolution of metals such as copper, nickel and cobalt from the sea nodules at initial pH in the range 4.0–5.0. With 10 min milling of particles of ?75 μm size, 86% material was reduced to ?10 μm size with a change in zeta potential from ?18 to ?34 mV. Above 95% copper, nickel and cobalt each was leached out in 15 days time from the nodules activated for 10 min at 5% (w/v) PD and 35 °C temperature with initial pH of 4.5; the biorecovery being almost similar when the material was activated for 30 min. In the case of nodules without activation, ?89% metal bioleaching was achieved in 25 days time at an initial pH of 4.5 under this condition. The mechano-chemical activation of sea nodules has thus influenced the bio-dissolution process, while providing a wider pH range available for processing of nodules with the involvement of organic acids such as oxalic and citric generated from the fungus.     

Leaching behaviour of natural and heat-treated brannerite-containing uranium ores in sulphate solutions with iron(III)

Uranium leaching tests were conducted on two naturally occurring, highly metamict brannerite ores from the Crockers Well and Roxby Downs deposits, South Australia. The ores were leached over a range of temperatures and Fe^(III) and H₂SO₄ concentrations. As well, samples of the ores were calcined at 1200 °C in air to investigate the effect of thermally induced recrystallisation on uranium dissolution. For the unheated samples, a maximum of ∼80% U dissolution was obtained using an Fe^(III) concentration of 12 g/L, an acid concentration of 150 g/L H₂SO₄ and a temperature of 95 °C. The heat treated samples performed poorly under identical conditions, with maximum uranium dissolution of <10% recorded. High uranium dissolution from natural brannerite can be achieved providing; (i) acid strength, oxidant strength and temperatures are maintained at elevated levels (compared to those traditionally used for uraninite leaching), and, (ii) the brannerite has not undergone any significant recrystallisation (e.g. through metamorphism).     

Atmospheric acid leaching of siliceous goethitic Ni laterite ore: Effect of solid loading and temperature

In this study, atmospheric acid leaching behaviour of siliceous goethitic nickel (Ni) laterite ore is investigated. Specifically, the effect of −200 μm feed solid loading (30 vs. 45 wt.%) and temperature (70 vs. 90 °C) on leach kinetics, acid consumption capacity and Ni and cobalt (Co) extraction was studied under isothermal, batch (4 h) leaching conditions at pH 1. Incongruent leaching was observed for constituent elements reflecting slow but steady release of value (Ni and Co) and some of gangue metals such as Fe, Mg and Al accompanied by faster and sharp release of Na and Si. Higher temperature and lower pulp solid loading, both led to a 40–50% increase in overall Ni and/or Co extraction and higher acid consumption. At 70 °C and 45 wt.% solid loading, Ni/Co extraction after 4 h was the lowest (∼14/16%) whilst the highest extraction (∼67/56%) was observed at 90 °C and 30 wt.% solid loading. Temperature appeared to have dramatic influence on Ni/Co and other impurity metals’ extractions revealing the chemical reaction controlled nature of the leaching. Higher solid loading and longer leaching time also both slowed down the leach kinetics. A two-stage chemical reactions-controlled leaching mechanism involving a faster initial leaching kinetics followed by a slower leaching at lower rate constants and higher activation energies was established for release of Ni, Co, Fe and Mg. The mechanism reflects the fast leaching of reactive host mineral phases (e.g., clays and Mg–silicates) during first 30 min followed by slow leaching of more refractory mineral phases (e.g., goethite and quartz) during the rest of leaching period. The findings provide a greater understanding for enhanced atmospheric acid leaching process of siliceous goethitic laterite ores.     

Enhancing Mg extraction from lizardite-rich serpentine for CO2 mineral sequestration

Carbon capture and storage by mineralisation (CCSM) is a promising technology that sequesters CO₂ from flue gases into stable mineral carbonates. Although the development of indirect pH swing processes (dissolution at acid pH and carbonation at basic pH) able to recycle the chemicals used are promising, there are still limitations in reaction rate of mineral dissolution being slow in view of a large deployment of the technology. The extraction of Mg from lizardite using magnesium bisulphate has been studied as a function of temperature, reagent concentration, solid to liquid ratio, thermal and mechanical pre-activation. Although the overall highest Mg extraction (95%) was obtained after 3 h, the reduction of the dissolution time to 1 h can consistently reduce the volumes to be treated per unit time leading to low capital costs in a hypothetical mineralisation plant. About 80% of Mg was extracted from lizardite in 1 h at 140 °C, 2.8 M NH₄HSO₄, particles <250 μm and a solid to liquid ratio of 100 g/l. At 140 °C, serpentine undergoes extensive structural modifications as indicated by XRD and FTIR analyses, producing amorphous silica and accelerating the kinetics of the reaction. Particles with diameter less than 250 μm were obtained by grinding the lizardite at 925 rpm for 10 min consuming 33 kW h/t_rock.     

Role of silicate phases during comminution of titania slag

Titania slag is the primary product of ilmenite smelting, and serves as a feedstock to the TiO₂ pigment industry. The fine material (smaller than 106 μm in diameter) which is produced during milling of titania slag is enriched in some impurities, notably SiO₂, Al₂O₃, K₂O and CaO. Investigation of microstructures of solidified slags confirmed that these oxides partition to the silicate phases which form during final solidification. The presence of silicates on the surfaces of particles in milled slag supports the suggestion that the silicates contribute to fracture during crushing and milling. No significant macro-segregation was found in the slag ingots.     

Chloride assisted leaching of chalcocite by oxygenated sulphuric acid via Cu(II)–OH–Cl

The beneficial effect of the addition of sodium chloride upon the leaching kinetics of complex iron–nickel–copper sulphides at elevated temperatures and oxygen pressures has been widely reported since the late 1970s, but the role of chloride is still being investigated or debated. Previous researchers have considered chloride as: (i) a complexing agent for cuprous ions; (ii) a surfactant that disperses the molten sulphur and thus removes passivation of the mineral surface by elemental sulphur during pressure leaching; and (iii) a reagent which increases the surface area and the porosity of the insoluble product layer on the surface. A proper understanding of the role of chloride based on the leaching of individual sulphides of known composition in the absence of host minerals at low pulp densities would be useful for the development of chloride assisted sulphate leaching processes for complex sulphide ores, concentrates, and mattes. In the present study evidence for the formation of basic salts of Cu(II) and Fe(III) during leaching are presented. The published rate data are analysed for the leaching of copper from mono-sized chalcocite particles in oxygenated sulphuric acid solutions maintained at 85 °C, a temperature lower than the melting point of sulphur. The initial leaching follows a shrinking particle (sphere) model, and the apparent rate constants are first order with respect to the concentration of dissolved oxygen and chloride. The intrinsic rate constant for the surface reaction (0.2 m s⁻¹) is two orders of magnitude larger than the calculated mass transfer coefficient of oxygen (3 × 10⁻³ m s⁻¹). The proposed reaction mechanism considers the formation of an interim Cu(II)(OH)Cl⁰ species which facilitates the leaching process.     

Iron solubilization during anaerobic growth of acidophilic microorganisms with a polymetallic sulfide ore

Acidithiobacillus ferrooxidans at 30 °C and Sulfobacillus thermosulfidooxidans at 47 °C were selected from a preliminary screening of various acidophiles for their ferric iron reduction capacities during anaerobic, autotrophic growth on sulfur. The selected cultures were used with a polymetallic sulfide ore under anoxic conditions to demonstrate enhanced solubilization of iron during leaching in shaken flasks and enhanced removal of iron from laboratory ore-leaching columns, compared to leaching with continuous aeration. Ore-associated, ferric iron-rich precipitates, which were formed under previously oxidizing conditions, were a potential influence on extraction of target metals and percolation through ore columns and were available as the source of ferric iron for anaerobic sulfur oxidation. Over twice as much iron was removed by moderate thermophiles when anoxic phases were introduced during the leaching. Enhanced removal of iron and some improvement in extraction of base metals from ore fragments were also demonstrated with a selected “Sulfolobus”-like strain during growth and leaching with alternating periods of aeration and anoxic conditions at 70 °C.     

Thiosulphate leaching of gold in the presence of ethylenediaminetetraacetic acid (EDTA)

The addition of low levels of ethylenediaminetetraacetic acid (EDTA) in the ammoniacal thiosulphate gold leach system lowered the catalytic cupric/cuprous redox equilibrium potential, hence the mixed solution potential and reduced the consumption of thiosulphate. In the leaching of pure gold, gold dissolution was enhanced in the presence of EDTA at a relatively low concentration, but excessive EDTA decreased gold dissolution. Raman analysis of the leached gold foil indicated that the stabilisation of thiosulphate by EDTA decreased the formation of the passivation layers of elemental sulphur and copper sulphide at the gold surface. In the leaching of a sulphide ore, the leaching kinetics and overall extractions of gold and silver were enhanced substantially, while the consumption of ammonium thiosulphate was reduced from 9.63 kg/t to 3.85 kg/t in the presence of 2.0 mM EDTA after 24 h leaching. This beneficial effect became more pronounced at a higher EDTA concentration. The enhanced gold and silver extractions by EDTA were attributed to the increase in the dissolution of gold and silver bearing sulphides, the stabilisation of copper and thiosulphate in leach solutions, the prevention of leaching passivation and the decrease in the interference of foreign heavy metal ions. The use of EDTA in the ammoniacal thiosulphate leaching system makes it practical to achieve satisfactory gold extraction over extended periods of leaching under low reagent concentrations, where the consumption of thiosulphate is low.     

Immobilization and ferrous iron bio-oxidation studies of a Leptospirillum sp. mixed-cell culture

Immobilization of a mixed bacterial culture (predominantly Leptospirillum sp.) on mechanically modified graphite surfaces and different types of activated carbon fiber supports (felt and textile; both silicated and non-silicated) was studied experimentally. Maximum cell coverage on graphite samples occurred on a surface roughness of 2.08 μm (3.9 × 10⁴ cells/mm²). In non-silicated samples the activated carbon fiber support with the greatest surface area per gram (felt) lead to the greatest number of immobilized microorganisms over a 10 h period (2.2 × 10⁴ cells/mm²). The silication significantly increased surface area in the fibrous matrix voids and thereby increased the number of immobilized microorganisms on both modified activated carbon felt and fabric. The silicated felt exhibited the greatest number of immobilized Leptospirillum sp. cells of all activated carbon fiber cathodes studied (2.9 × 10⁴ cells/mm²). Physical property and elemental analyses of silicated samples indicated that other methods of augmenting bacterial immobilization should be explored as silication increased electrical resistance of the samples 100 fold. Leptospirillum sp. immobilized on unmodified activated carbon felt yielded the maximum experimentally observed rate of ferrous iron bio-oxidation (～900 mg/L h).     

Extraction of indium from zinc plant residues

The main purpose of this study was to extract indium from the Irankoh zinc plant residue. The Irankoh zinc plant residue contained 145 ppm indium. The optimum conditions for leaching of indium and reduction of ferric ion in reductive leaching were obtained at temperature of 90 °C for a leaching duration of 3 h with sulfuric acid concentration of 100 g/L and the amount of required sodium sulfide for reduction of ferric was 1.5 times of stoichiometric quantity of iron. Then, to prepare concentrated indium solution, indium was selectively precipitated from the leach solution. The pH of leach solution was adjusted to 6 with ammonia solution in 90 °C for selective indium precipitation, and reaction time was considered to be 10 min. Then the resulting precipitation was dissolved using hot sulfuric acid solution, and the solution was subject to solvent extraction and cementation using zinc powder to recover indium.     

Recovery of zinc and cadmium from industrial waste by leaching/cementation

Metallic zinc production from sulfide zinc ore is comprised by the stages of ore concentration, roasting, leaching, liquor purification, electrolysis and melting. During the leaching stage with sulfuric acid, other metals present in the ore in addition to zinc are also leached. The sulfuric liquor obtained in the leaching step is purified through impurities cementation. This step produces a residue with a high content of zinc, cadmium and copper, in addition to lead, cobalt and nickel. This paper describes the study of selective dissolution of zinc and cadmium present in the residue, followed by the segregation of those metals by cementation. The actual sulfuric solution, depleted from the electrolysis stage of metallic zinc production, was used as leaching agent. Once the leaching process variables were optimized, a liquor containing 141 g/L Zn, 53 g/L Cd, 0.002 g/L Cu, 0.01 g/L Co and 0.003 g/L Ni was obtained from a residue containing 30 wt.% Zn, 26 wt.% Cd, 7 wt.% Cu, 0.35 wt.% Co and 0.32 wt.% Ni. The residue mass reduction exceeded 80 wt.%. Cementation studies investigated the influence of temperature, reaction time, zinc concentration in feeding solution, pH of feeding solution and metallic zinc excess. After that such variables were optimized, more than 99.9% of cadmium present in liquor was recovered in the form of metallic cadmium with 97 wt.% purity. A filtrate (ZnSO₄ solution) containing 150 g/L Zn and 0.005 g/L Cd capable of feeding the electrolysis zinc stage was also obtained.